04 Lecture

Lecture Presentation
Chapter 4
Reactions in
Aqueous Solution
James F. Kirby
Quinnipiac University
Hamden, CT
Aqueous
Reactions
© 2015 Pearson Education, Inc.

Solutions
• Solutions are defined as
homogeneous mixtures of
two or more pure
substances.
• The solvent is present in
greatest abundance.
• All other substances are
solutes.
• When water is the solvent,
the solution is called an
aqueous solution. Aqueous
Reactions

Aqueous Solutions
• Substances can dissolve in water by different ways:
 Ionic Compounds dissolve by dissociation, where
water surrounds the separated ions.
 Molecular compounds interact with water, but most do
NOT dissociate.
 Some molecular substances react with water when
they dissolve.
Aqueous
Reactions

Dissolution of a solid in a liquid
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Copyright 4
Electrolytes and Nonelectrolytes
• An electrolyte is a substance that dissociates

into ions when dissolved in water.
• A nonelectrolyte may dissolve in water, but it
does not dissociate into ions when it does so.
Aqueous
Reactions

Electrolytes
• A strong electrolyte dissociates completely when

dissolved in water.
• A weak electrolyte only dissociates partially when
dissolved in water.
• A nonelectrolyte does NOT dissociate in water. Aqueous
Reactions

Solubility of Ionic Compounds
• Not all ionic compounds dissolve in water.
• A list of solubility rules is used to decide
what combination of ions will dissolve.
Aqueous
Reactions

Precipitation Reactions
When two solutions containing soluble salts are
mixed, sometimes an insoluble salt will be
produced. A salt “falls” out of solution, like snow
out of the sky. This solid is called a precipitate.
Aqueous
Reactions

Precipitation of Silver Chloride

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Reactions
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Copyright 9
Metathesis (Exchange) Reactions
• Metathesis comes from a Greek word that
means “to transpose.”
• It appears as though the ions in the reactant
compounds exchange, or transpose, ions, as
seen in the equation below.
AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)
Aqueous
Reactions

Completing and Balancing
Metathesis Equations
• Steps to follow
1) Use the chemical formulas of the reactants
to determine which ions are present.
2) Write formulas for the products: cation from
one reactant, anion from the other. Use
charges to write proper subscripts.
3) Check your solubility rules. If either product
is insoluble, a precipitate forms.
4) Balance the equation. Aqueous
Reactions

Ways to Write Metathesis Reactions
1) Molecular equation
2) Complete ionic equation
3) Net ionic equation
Aqueous
Reactions

Molecular Equation
The molecular equation lists the reactants

and products without indicating the ionic
nature of the compounds.
AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)
Aqueous
Reactions

Complete Ionic Equation
• In the complete ionic equation all strong
electrolytes (strong acids, strong bases, and soluble
ionic salts) are dissociated into their ions.
• This more accurately reflects the species that are
found in the reaction mixture.
Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq) 

AgCl(s) + K+(aq) + NO3−(aq)
Aqueous
Reactions

Net Ionic Equation
• To form the net ionic equation, cross out anything
that does not change from the left side of the
equation to the right.
• The ions crossed out are called spectator ions, K+
and NO3−, in this example.
• The remaining ions are the reactants that form the
product—an insoluble salt in a precipitation reaction,
as in this example.
Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq) 
AgCl(s) + K+(aq) + NO3−(aq)
Aqueous
Reactions

Writing Net Ionic Equations
1. Write a balanced molecular equation.
2. Dissociate all strong electrolytes.
3. Cross out anything that remains
unchanged from the left side to the
right side of the equation.
4. Write the net ionic equation with the
species that remain.
Aqueous
Reactions

Acids
• The Swedish physicist
and chemist S. A.
Arrhenius defined acids
as substances that
increase the
concentration of H+
when dissolved in water.
• Both the Danish chemist
J. N. Brønsted and the
British chemist T. M.
Lowry defined them as
proton donors. Aqueous
Reactions

Bases
• Arrhenius defined bases
as substances that
increase the
concentration of OH−
when dissolved in water.
• Brønsted and Lowry
defined them as proton
acceptors.
Aqueous
Reactions

Strong or Weak?
• Strong acids completely dissociate in water;
weak acids only partially dissociate.
• Strong bases dissociate to metal cations and
hydroxide anions in water; weak bases only
partially react to produce hydroxide anions.
Aqueous
Reactions

Acid-Base Reactions
In an acid–base reaction, the acid (H2O above)

donates a proton (H+) to the base (NH3 above).
Reactions between an acid and a base are called
neutralization reactions.
When the base is a metal hydroxide, water and a
salt (an ionic compound) are produced.
Aqueous
Reactions

Neutralization Reactions
When a strong acid (like HCl) reacts with a strong
base (like NaOH), the net ionic equation is circled
below:
HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)
H+(aq) + Cl−(aq) + Na+(aq) + OH−(aq) 

Na+(aq) + Cl−(aq) + H2O(l)
H+(aq) + OH−(aq)  H2O(l)

Aqueous
Reactions

Neutralization of a Strong Acid by a Strong Base

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Gas-Forming Reactions
 Some metathesis reactions do not give the

product expected.
 When a carbonate or bicarbonate reacts with
an acid, the products are a salt, carbon
dioxide, and water.
CaCO3(s) + 2 HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)

NaHCO3(aq) + HBr(aq) NaBr(aq) + CO2(g) + H2O(l)
Aqueous
Reactions

Gas-Forming Reactions
This reaction gives the predicted product, but
you had better carry it out in the hood—the gas
produced has a foul odor!
Na2S(aq) + H2SO4(aq)  Na2SO4(aq) + H2S(g)
Aqueous
Reactions

Oxidation-Reduction Reactions
• Loss of electrons is oxidation.

• Gain of electrons is reduction.
• One cannot occur without the other.
• The reactions are often called redox reactions. Aqueous
Reactions

Oxidation Numbers
To determine if an oxidation–reduction
reaction has occurred, we assign an
oxidation number to each element in a
neutral compound or charged entity.
Aqueous
Reactions

Rules to Assign Oxidation Numbers
• Elements in their elemental form have

an oxidation number of zero.
• The oxidation number of a monatomic
ion is the same as its charge.
Aqueous
Reactions

• Nonmetals tend to have negative

oxidation numbers, although some are
positive in certain compounds or ions.
– Oxygen has an oxidation number of −2,
except in the peroxide ion, in which it has
an oxidation number of −1.
– Hydrogen is −1 when bonded to a metal,
+1 when bonded to a nonmetal.
Aqueous
Reactions

• Nonmetals tend to have negative

oxidation numbers, although some are
positive in certain compounds or ions.
– Fluorine always has an oxidation number
of −1.
– The other halogens have an oxidation
number of −1 when they are negative; they
can have positive oxidation numbers, most
notably in oxyanions.
Aqueous
Reactions

• The sum of the oxidation numbers in a

neutral compound is zero.
• The sum of the oxidation numbers in a
polyatomic ion is the charge on the ion.
Aqueous
Reactions

Displacement Reactions
In displacement
reactions, ions
oxidize an
element.
In this reaction,
silver ions oxidize
copper metal:
Cu(s) + 2 Ag+(aq)  Cu2+(aq) + 2 Ag(s)
The reverse reaction does NOT occur. Why not? Aqueous

Reactions

Activity Series
• Elements
higher on the
activity series
are more
reactive.
• They are
more likely to
exist as ions.
Aqueous
Reactions

Metal/Acid Displacement Reactions
• The elements above hydrogen will react
with acids to produce hydrogen gas.
• The metal is oxidized to a cation.
Aqueous
Reactions

Molarity
• The quantity of solute in a solution can matter to
a chemist.
• We call the amount dissolved its concentration.
• Molarity is one way to measure the
concentration of a solution:
moles of solute
Molarity (M) =
volume of solution in liters
Aqueous
Reactions

Mixing a Solution
• To create a solution of a known molarity, weigh out
a known mass (and, therefore, number of moles) of
the solute.
• Then add solute to a volumetric flask, and add
solvent to the line on the neck of the flask.
Aqueous
Reactions

Dilution
• One can also dilute a more concentrated
solution by
– using a pipet to deliver a volume of the solution to a
new volumetric flask, and
– adding solvent to the line on the neck of the new flask.
Aqueous
Reactions

Dilution
The molarity of the new solution can be
determined from the equation
Mc  Vc = Md  Vd,
where Mc and Md are the molarity of the
concentrated and dilute solutions,
respectively, and Vc and Vd are the
volumes of the two solutions.
Aqueous
Reactions

Using Molarities in
Stoichiometric Calculations
Aqueous
Reactions

Titration
A titration is an analytical technique in which one
can calculate the concentration of a solute in a
solution.
Aqueous
Reactions

Titration
• A solution of known concentration, called a

standard solution, is used to determine the
unknown concentration of another solution.
• The reaction is complete at the equivalence
point. Aqueous
Reactions

Sample Exercise 4.1 Relating Relative Numbers of Anions
and Cations to Chemical Formulas
The accompanying diagram represents an aqueous solution of either MgCl 2, KCl, or K2SO4.
Which solution does the drawing best represent?
Solution
Analyze We are asked to associate the charged spheres in the diagram
with ions present in a solution of an ionic substance.
Plan We examine each ionic substance given to determine the relative numbers and
charges of its ions. We then correlate these ionic species with the ones shown in the diagram.
Solve The diagram shows twice as many cations as anions, consistent with the formulation K2SO4.
Check Notice that the net charge in the diagram is zero, as it must be if it is to represent an ionic substance.
Practice Exercise 1
If you have an aqueous solution that contains 1.5 moles of HCl, how many moles of ions are in the solution?
(a) 1.0, (b) 1.5, (c) 2.0, (d) 2.5, (e) 3.
Practice Exercise 2
If you were to draw diagrams representing aqueous solutions of (a) NiSO4, (b) Ca(NO3)2, (c) Na3PO4,
(d) Al2(SO4)3, how many anions would you show if each diagram contained six cations?
Chemistry: The Central Science, 13th Edition © 2015 Pearson Education, Inc.
Brown/LeMay/Bursten/Murphy/Woodward/Stoltzfus
Sample Exercise 4.2 Using Solubility Rules
Classify these ionic compounds as soluble or insoluble in water: (a) sodium carbonate, Na2CO3,
(b) lead sulfate, PbSO4.
Solution
Analyze We are given the names and formulas of two ionic compounds and asked to predict whether they are
soluble or insoluble in water.
Plan We can use Table 4.1 to answer the
question. Thus, we need to focus on the
anion in each compound because
the table is organized by anions.
(a) According to Table 4.1, most carbonates are insoluble. But carbonates of the alkali metal cations (such as
sodium ion) are an exception to this rule and are soluble. Thus, Na2CO3 is soluble in water.
(b) Table 4.1 indicates that although most sulfates are water soluble, the sulfate of Pb 2+ is an exception.
Thus, PbSO4 is insoluble in water.
Sample Exercise 4.2 Using Solubility Rules
Continued
Practice Exercise 1
Which of the following compounds is insoluble in water?
(a) (NH4)2S, (b) CaCO3, (c) NaOH, (d) Ag2SO4, (e) Pb(CH3COO)2.
Practice Exercise 2
Classify the following compounds as soluble or insoluble in water: (a) cobalt(II) hydroxide, (b) barium nitrate,
(c) ammonium phosphate.
Sample Exercise 4.3 Predicting a Metathesis Reaction
(a) Predict the identity of the precipitate that forms when aqueous solutions of BaCl 2 and K2SO4 are mixed.
(b) Write the balanced chemical equation for the reaction.
Solution
Analyze We are given two ionic reactants and asked to predict the insoluble product that they form.
Plan We need to write the ions present in the reactants
and exchange the anions between the two cations.
Once we have written the chemical formulas for these
products, we can use Table 4.1 to determine which is
insoluble in water. Knowing the products also allows
us to write the equation for the reaction.
(a) The reactants contain Ba2+, Cl–, K+, and SO42− ions. Exchanging the anions gives us BaSO4 and KCl. According
to Table 4.1, most compounds of SO42– are soluble but those of Ba2+ are not. Thus, BaSO4 is insoluble and
will precipitate from solution. KCl is soluble.
(b) From part (a) we know the chemical formulas of the products, BaSO4 and KCl. The balanced equation is
Sample Exercise 4.3 Predicting a Metathesis Reaction
Continued
Practice Exercise 1
Yes or No: Will a precipitate form when solutions of Ba(NO3)2 and KOH are mixed?
Practice Exercise 2
(a) What compound precipitates when aqueous solutions of Fe 2(SO4)3 and LiOH are mixed? (b) Write a balanced
equation for the reaction.
Sample Exercise 4.4 Writing a Net Ionic Equation
Write the net ionic equation for the precipitation reaction that occurs when aqueous solutions of calcium chloride
and sodium carbonate are mixed.
Solution
Analyze Our task is to write a net ionic equation for a precipitation reaction, given the names of the reactants
present in solution.
Plan We write the chemical formulas of the reactants and products and then determine which product is insoluble.
We then write and balance the molecular equation. Next, we write each soluble strong electrolyte as separated ions to
obtain the complete ionic equation. Finally, we eliminate the spectator ions to obtain the net ionic equation.
Solve Calcium chloride is composed of calcium ions,
Ca2+, and chloride ions, Cl–; hence, an aqueous solution
of the substance is CaCl2(aq). Sodium carbonate is
composed of Na+ ions and CO32– ions; hence, an
aqueous solution of the compound is Na2CO3(aq).
In the molecular equations for precipitation reactions,
the anions and cations appear to exchange partners.
Thus, we put Ca2+ and CO32– together to give CaCO3
and Na+ and Cl– together to give NaCl. According to
the solubility guidelines in Table 4.1, CaCO3 is insoluble
and NaCl is soluble. The balanced molecular equation is
Continued
In a complete ionic equation, only dissolved strong electrolytes (such as soluble ionic compounds) are written as
separate ions. As the (aq) designations remind us, CaCl2, Na2CO3, and NaCl are all dissolved in the solution.
Furthermore, they are all strong electrolytes. CaCO3 is an ionic compound, but it is not soluble. We do not write the
formula of any insoluble compound as its component ions. Thus, the complete ionic equation is
The spectator ions are Na+ and Cl–. Canceling them gives the following net ionic equation:
Check We can check our result by confirming that both the elements and the electric charge are balanced. Each side
has one Ca, one C, and three O, and the net charge on each side equals 0.
Comment If none of the ions in an ionic equation is removed from solution or changed in some way, all ions are
spectator ions and a reaction does not occur.
Practice Exercise 1
What happens when you mix an aqueous solution of sodium nitrate with an aqueous solution of barium chloride?
(a) There is no reaction; all possible products are soluble. (b) Only barium nitrate precipitates. (c) Only sodium
chloride precipitates. (d) Both barium nitrate and sodium chloride precipitate. (e) Nothing; barium chloride is not
soluble and it stays as a precipitate.
Continued
Practice Exercise 2
Write the net ionic equation for the precipitation reaction that occurs when aqueous solutions of silver nitrate and
potassium phosphate are mixed.
Sample Exercise 4.5 Comparing Acid Strengths
The following diagrams represent aqueous solutions of acids HX, HY, and HZ, with water molecules omitted for
clarity. Rank the acids from strongest to weakest.
Solution
Analyze We are asked to rank three acids from strongest to weakest, based on schematic drawings of their solutions.
Plan We can determine the relative numbers of uncharged molecular species in the diagrams. The strongest acid is the
one with the most H+ ions and fewest undissociated molecules in solution. The weakest acid is the one with the
largest number of undissociated molecules.
Solve The order is HY > HZ > HX. HY is a strong acid because it is totally ionized (no HY molecules in solution),
whereas both HX and HZ are weak acids, whose solutions consist of a mixture of molecules and ions. Because HZ
contains more H+ ions and fewer molecules than HX, it is a stronger acid.
Sample Exercise 4.5 Comparing Acid Strengths
Continued
Practice Exercise 1
A set of aqueous solutions are prepared containing different acids at the same concentration: acetic acid, chloric acid
and hydrobromic acid. Which solution(s) are the most electrically conductive? (a) chloric acid, (b) hydrobromic acid,
(c) acetic acid, (d) both chloric acid and hydrobromic acid, (e) all three solutions have the same electrical
conductivity.
Practice Exercise 2
Imagine a diagram showing 10 Na+ ions and 10 OH– ions. If this solution were mixed with the one pictured above for
HY, what species would be present in a diagram that represents the combined solutions after any possible reaction?
Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Classify these dissolved substances as a strong electrolyte, weak electrolyte, or nonelectrolyte: CaCl2, HNO3,
C2H5OH (ethanol), HCOOH (formic acid), KOH.
Solution
Analyze We are given several chemical formulas and asked to classify each substance as a strong electrolyte, weak
electrolyte, or nonelectrolyte.
Plan The approach we take is outlined in Table 4.3. We
can predict whether a substance is ionic or molecular
based on its composition. As we saw in Section 2.7, most
ionic compounds we encounter in this text are composed
of a metal and a nonmetal, whereas most molecular
compounds are composed only of nonmetals.
Solve Two compounds fit the criteria for ionic compounds:
CaCl2 and KOH. Because Table 4.3 tells us that all ionic
compounds are strong electrolytes, that is how we classify
these two substances. The three remaining compounds are
molecular. Two of these molecular substances, HNO3 and
HCOOH, are acids. Nitric acid, HNO3, is a common strong
acid, as shown in Table 4.2, and therefore is a strong
electrolyte. Because most acids are weak acids, our best
guess would be that HCOOH is a weak acid (weak
electrolyte), which is in fact the case. The remaining
molecular compound, C2H5OH, is neither an acid nor a base, so it is a nonelectrolyte.
Sample Exercise 4.6 Identifying Strong, Weak, and Nonelectrolytes
Continued
Comment Although ethanol, C2H5OH, has an OH group, it is not a metal hydroxide and therefore not a base.
Rather ethanol is a member of a class of organic compounds that have C—OH bonds, which are known as alcohols.
(Section 2.9) Organic compounds containing the COOH group are called carboxylic acids (Chapter 16). Molecules
that have this group are weak acids.
Practice Exercise 1
Which of these substances, when dissolved in water, is a strong electrolyte? (a) ammonia, (b) hydrofluoric acid,
(c) folic acid, (d) sodium nitrate, (e) sucrose.
Practice Exercise 2
Consider solutions in which 0.1 mol of each of the following compounds is dissolved in 1 L of water: Ca(NO 3)2
(calcium nitrate), C6H12O6 (glucose), NaCH3COO (sodium acetate), and CH3COOH (acetic acid). Rank the solutions
in order of increasing electrical conductivity, knowing that the greater the number of ions in solution, the greater the
conductivity.
Sample Exercise 4.7 Writing Chemical Equations for a Neutralization
Reaction
For the reaction between aqueous solutions of acetic acid (CH3COOH) and barium hydroxide, Ba(OH2), write
(a) the balanced molecular equation, (b) the complete ionic equation, (c) the net ionic equation.
Solution
Analyze We are given the chemical formulas for an acid and a base and asked to write a balanced molecular equation,
a complete ionic equation, and a net ionic equation for their neutralization reaction.
Plan As Equation 4.12 and the italicized statement that
follows it indicate, neutralization reactions form two
products, H2O and a salt. We examine the cation of the
base and the anion of the acid to determine the
composition of the salt.
Solve
(a) The salt contains the cation of the base (Ba2+) and
the anion of the acid (CH3COO–). Thus, the salt
formula is Ba(CH3COO)2. According to Table 4.1,
this compound is soluble in water. The unbalanced
molecular equation for the neutralization reaction is
Reaction
Continued
To balance this equation, we must provide two molecules of CH3COOH to furnish the two
CH3COO– ions and to supply the two H+ ions needed to combine with the two the two H+ ions
needed to combine with the two OH– ions of the base. The balanced molecular equation is
(b) To write the complete ionic equation, we identify the strong electrolytes and break them into ions. In this case
Ba(OH2) and Ba(CH3COO)2 are both water-soluble ionic compounds and hence strong water-soluble ionic
compounds and hence strong
(c) Eliminating the spectator ion, Ba2+, and simplifying coefficients gives the net ionic equation:
Reaction
Continued
Check We can determine whether the molecular equation is balanced by counting the number of atoms of each kind
on both sides of the arrow (10 H, 6 O, 4 C, and 1 Ba on each side). However, it is often easier to check equations by
counting groups: There are 2 CH3COO groups, as well as 1 Ba, and 4 additional H atoms and 2 additional O atoms on
each side of the equation. The net ionic equation checks out because the numbers of each kind of element and the net
charge are the same on both sides of the equation.
Practice Exercise 1
Which is the correct net ionic equation for the reaction of aqueous ammonia with nitric acid?
Practice Exercise 2
For the reaction of phosphorous acid (H3PO3) and potassium hydroxide (KOH), write (a) the balanced molecular
equation and (b) the net ionic equation.
Sample Exercise 4.8 Determining Oxidation Numbers
Determine the oxidation number of sulfur in (a) H2S, (b) S8, (c) SCl2, (d) Na2SO3, (e) SO42–.
Solution
Analyze We are asked to determine the oxidation number of sulfur in two molecular species, in the elemental form,
and in two substances containing ions.
Plan In each species the sum of oxidation numbers of all the atoms must equal the charge on the species. We will use
the rules outlined previously to assign oxidation numbers.
Solve
(a) When bonded to a nonmetal, hydrogen has an oxidation number of +1. Because the H 2S molecule is neutral, the
sum of the oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have 2(+1) + x = 0.
Thus, S has an oxidation number of –2.
(b) Because S8 is an elemental form of sulfur, the oxidation number of S is 0.
(c) Because SCl2 is a binary compound, we expect chlorine to have an oxidation number of –1. The sum of the
oxidation numbers must equal zero. Letting x equal the oxidation number of S, we have x + 2(–1) = 0.
Consequently, the oxidation number of S must be +2.
(d) Sodium, an alkali metal, always has an oxidation number of +1 in its compounds. Oxygen commonly has an
oxidation state of –2. Letting x equal the oxidation number of S, we have 21 + 12 + x + 31 – 22 = 0. Therefore,
the oxidation number of S in this compound (Na2SO3) is +4.
(e) The oxidation state of O is –2. The sum of the oxidation numbers equals –2, the net charge of the SO42– ion. Thus,
we have x + 41 – 22 = –2. From this relation we conclude that the oxidation number of S in this ion is +6.
Sample Exercise 4.8 Determining Oxidation Numbers
Continued
Comment These examples illustrate that the oxidation number of a given element depends on the compound in which
it occurs. The oxidation numbers of sulfur, as seen in these examples, range from –2 to +6.
Practice Exercise 1
In which compound is the oxidation state of oxygen –1? (a) O2, (b) H2O, (c) H2SO4, (d) H2O2, (e) KCH3COO.
Practice Exercise 2
What is the oxidation state of the boldfaced element in (a) P2O5, (b) NaH, (c) Cr2O72–, (d) SnBr4, (e) BaO2?
Sample Exercise 4.9 Writing Equations for Oxidation-Reduction
Reactions
Write the balanced molecular and net ionic equations for the reaction of aluminum with hydrobromic acid.
Solution
Analyze We must write two equations—molecular and net ionic—for the redox reaction between a metal and an acid
Plan Metals react with acids to form salts and H2 gas. To write the balanced equations, we must write the chemical
formulas for the two reactants and then determine the formula of the salt, which is composed of the cation formed by
the metal and the anion of the acid.
Solve The reactants are Al and HBr. The cation formed by Al is Al3+ and the anion from hydrobromic acid is Br–.
Thus, the salt formed in the reaction is AlBr3. Writing the reactants and products and the balancing the equation gives
the molecular equation:
Both HBr and AlBr3 are soluble strong electrolytes. Thus, the complete ionic equation is
Because Br– is a spectator ion, the net ionic equation is
Sample Exercise 4.9 Writing Equations for Oxidation-Reduction
Reactions
Continued
Comment The substance oxidized is the aluminum metal because its oxidation state changes from 0 in the metal to
+3 in the cation, thereby increasing in oxidation number. The H+ is reduced because its oxidation state changes from
+1 in the acid to 0 in H2.
Practice Exercise 1
Which of the following statements is true about the reaction between zinc and copper sulfate? (a) Zinc is oxidized,
and copper on is reduced. (b) Zinc is reduced, and copper ion is oxidized. (c) All reactants and products are soluble
strong electrolytes. (d) The oxidation state of copper in copper sulfate is 0. (e) More than one of the previous choices
are true.
Practice Exercise 2
(a) Write the balanced molecular and net ionic equations for the reaction between magnesium and cobalt(II) sulfate.
(b) What is oxidized and what is reduced in the reaction?
Sample Exercise 4.10 Determining When an Oxidation-Reduction
Reaction Can Occur
Will an aqueous solution of iron(II) chloride oxidize magnesium metal? If so, write the balanced molecular and
net ionic equations for the reaction.
Solution
Analyze We are given two substances—an aqueous salt, FeCl2, and a metal, Mg—and asked if they react with
each other.
Plan A reaction occurs if the reactant that is a metal in its elemental form (Mg) is located above the reactant that is a
metal in its oxidized form (Fe2+) in Table 4.5. If the reaction occurs, the Fe2+ ion in FeCl2 is reduced to Fe, and the Mg
is oxidized to Mg2+.
Solve Because Mg is above Fe in the table, the reaction occurs. To write the formula for the salt produced in the
reaction, we must remember the charges on common ions. Magnesium is always present in compounds as Mg 2+; the
chloride ion is Cl–. The magnesium salt formed in the reaction is MgCl 2, meaning the balanced molecular equation is
Both FeCl2 and MgCl2 are soluble strong electrolytes and can be written in ionic form, which shows us that Cl– is a
spectator ion in the reaction. The net ionic equation is
The net ionic equation shows that Mg is oxidized and Fe 2+ is reduced in this reaction.
Sample Exercise 4.10 Determining When an Oxidation-Reduction
Reaction Can Occur
Continued
Check Note that the net ionic equation is balanced with respect to both charge and mass.
Practice Exercise 1
Which of these metals is the easiest to oxidize? (a) gold, (b) lithium, (c) iron, (d) sodium, (e) aluminum.
Practice Exercise 2
Which of the following metals will be oxidized by Pb(NO3)2: Zn, Cu, Fe?
Sample Exercise 4.11 Calculating Molarity
Calculate the molarity of a solution made by dissolving 23.4 g of sodium sulfate (Na2SO4) in enough water to
form 125 mL of solution.
Solution
Analyze We are given the number of grams of solute (23.4 g), its chemical formula (Na 2SO4), and the volume of the
solution (125 mL) and asked to calculate the molarity of the solution.
Plan We can calculate molarity using Equation 4.32. To do so, we must convert the number of grams of solute to
moles and the volume of the solution from milliliters to liters.
Solve The number of moles of Na2SO4 is
obtained by using its molar mass:
Converting the volume of the solution to liters:
Thus, the molarity is

Check Because the numerator is only slightly larger than the denominator, it is reasonable for the answer to be a little
over 1 M. The units (mol/L) are appropriate for molarity, and three significant figures are appropriate for the answer
because each of the initial pieces of data had three significant figures.
Sample Exercise 4.11 Calculating Molarity
Continued
Practice Exercise 1
What is the molarity of a solution that is made by dissolving 3.68 g of sucrose (C 12H22O11) in sufficient water to form
275.0 mL of solution? (a) 13.4 M, (b) 7.43 × 10–2 M, (c) 3.91 × 10–2 M, (d) 7.43 × 10–5 M, (e) 3.91 × 10–5 M.
Practice Exercise 2
Calculate the molarity of a solution made by dissolving 5.00 g of glucose (C 6H12O6) in sufficient water to form
exactly 100 mL of solution.
Sample Exercise 4.12 Calculating Molar Concentrations of Ions
What is the molar concentration of each ion present in a 0.025 M aqueous solution of calcium nitrate?
Solution
Analyze We are given the concentration of the ionic compound used to make the solution and asked to determine the
concentrations of the ions in the solution.
Plan We can use the subscripts in the chemical formula of the compound to determine the relative ion concentrations.
Solve Calcium nitrate is composed of calcium ions (Ca)+2 and nitrate ions (NO3–), so its chemical formula is
Ca(NO3)2. Because there are two NO3– ions for each Ca2+ ion, each mole of Ca(NO3)2 that dissolves dissociates into
1 mol of Ca2+ and 2 mol of NO3–. Thus, a solution that is 0.025 M in Ca(NO3)2 is 0.025 M in Ca2+
and 2 × 0.025 M = 0.050 M in NO3–:
Check The concentration of NO3– ions is twice that of Ca2+ ions, as the subscript 2 after the NO3– in the chemical
formula Ca(NO3)2 suggests.
Practice Exercise 1
What is the ratio of the concentration of potassium ions to the concentration of carbonate ions in a 0.015 M solution
of potassium carbonate? (a) 1:0.015, (b) 0.015:1, (c) 1:1, (d) 1:2, (e) 2:1.
Practice Exercise 2
What is the molar concentration of K+ ions in a 0.015 M solution of potassium carbonate?
Sample Exercise 4.13 Using Molarity to Calculate Grams of Solute
How many grams of Na2SO4 are required to make 0.350 L of 0.500 M Na2SO4?
Solution
Analyze We are given the volume of the solution (0.350 L), its concentration (0.500 M), and the identity of the solute
Na2SO4 and asked to calculate the number of grams of the solute in the solution.
Plan We can use the definition of molarity (Equation 4.32) to determine the number of moles of solute, and then
convert moles to grams using the molar mass of the solute.
Solve Calculating the moles of Na2SO4 using the molarity and volume of solution gives
Because each mole of Na2SO4 has a mass of 142.1 g, the required number of grams of Na 2SO4 is
Sample Exercise 4.13 Using Molarity to Calculate Grams of Solute
Continued
Check The magnitude of the answer, the units, and the number of significant figures are all appropriate.
Practice Exercise 1
What is the concentration of ammonia in a solution made by dissolving 3.75 g of ammonia in 120.0 L of water?
(a) 1.84 × 10–3 M, (b) 3.78 × 10–2 M, (c) 0.0313 M, (d) 1.84 M, (e) 7.05 M.
Practice Exercise 2
(a) How many grams of Na2SO4 are there in 15 mL of 0.50 M Na2SO4? (b) How many milliliters of 0.50 M Na2SO4
solution are needed to provide 0.038 mol of this salt?
Sample Exercise 4.14 Preparing a Solution by Dilution
How many milliliters of 3.0 M H2SO4 are needed to make 450 mL of 0.10 M H2SO4?
Solution
Analyze We need to dilute a concentrated solution. We are given the molarity of a more concentrated solution (3.0 M)
and the volume and molarity of a more dilute one containing the same solute (450 mL of 0.10 M solution). We must
calculate the volume of the concentrated solution needed to prepare the dilute solution.
Plan We can calculate the number of moles of solute, H2SO4, in the dilute solution and then calculate the volume of
the concentrated solution needed to supply this amount of solute. Alternatively, we can directly apply Equation 4.34.
Let’s compare the two methods.
Solve Calculating the moles of H2SO4 in the dilute solution: Converting the volume of the solution to liters:
Calculating the volume of the concentrated solution that contains 0.045 mol H 2SO4:
Converting liters to milliliters gives 15 mL.
Sample Exercise 4.14 Preparing a Solution by Dilution
Continued
If we apply Equation 4.34, we get the same result:
Either way, we see that if we start with 15 mL of 3.0 M H2SO4 and dilute it to a total volume of 450 mL, the desired
0.10 M solution will be obtained.
Check The calculated volume seems reasonable because a small volume of concentrated solution is used to prepare a
large volume of dilute solution.
Comment The first approach can also be used to find the final concentration when two solutions of different
concentrations are mixed, whereas the second approach, using Equation 4.34, can be used only for diluting a
concentrated solution with pure solvent.
Practice Exercise 1
What volume of a 1.00 M stock solution of glucose must be used to make 500.0 mL of a 1.75 ✕ 10–2 M glucose
solution in water? (a) 1.75 mL, (b) 8.75 mL, (c) 48.6 mL, (d) 57.1 mL, (e) 28,570 mL.
Practice Exercise 2
(a) What volume of 2.50 M lead(II) nitrate solution contains 0.0500 mol of Pb2+? (b) How many milliliters of 5.0 M
K2Cr2O7 solution must be diluted to prepare 250 mL of 0.10 M solution? (c) If 10.0 mL of a 10.0 M stock solution of
NaOH is diluted to 250 mL, what is the concentration of the resulting stock solution?
Sample Exercise 4.15 Using Mass Relations in a Neutralization
Reaction
How many grams of Ca(OH)2 are needed to neutralize 25.0 mL of 0.100 M HNO3?
Solution
Analyze The reactants are an acid, HNO3, and a base, Ca(OH)2. The volume and molarity of HNO3 are given, and we
are asked how many grams of Ca(OH)2 are needed to neutralize this quantity of HNO3.
Plan Following the steps outlined by the green arrows in Figure 4.17, we use the molarity and volume of the HNO3
solution (substance B in Figure 4.17) to calculate the number of moles of HNO 3. We then use the balanced equation to
relate moles of HNO3 to moles of Ca(OH)2 (substance A). Finally, we use the molar mass to convert moles to grams
of Ca(OH)2:
Solve The product of the molar concentration of a solution and its volume in liters gives the number of moles
of solute:
Because this is a neutralization reaction, HNO3 and Ca(OH)2 react to form H2O and the salt containing Ca2+
and NO3–:
Sample Exercise 4.15 Using Mass Relations in a Neutralization
Reaction
Continued
Check The answer is reasonable because a small volume of dilute acid requires only a small amount of base to
neutralize it.
Practice Exercise 1
How many milligrams of sodium sulfide are needed to completely react with 25.00 mL of a 0.0100 M aqueous
solution of cadmium nitrate, to form a precipitate of CdS(s)? (a) 13.8 mg, (b) 19.5 mg, (c) 23.5 mg, (d) 32.1 mg,
(e) 39.0 mg.
Practice Exercise 2
(a) How many grams of NaOH are needed to neutralize 20.0 mL of 0.150 M H2SO4 solution? (b) How many
liters of 0.500 M HCl(aq) are needed to react completely with 0.100 mol of Pb(NO3)2(aq), forming a precipitate
of PbCl2(s)?
Sample Exercise 4.16 Determining Solution Concentration by an
Acid–Base Titration
One commercial method used to peel potatoes is to soak them in a NaOH solution for a short time and then
remove the potatoes and spray off the peel. The NaOH concentration is normally 3 to 6 M, and the solution must
be analyzed periodically. In one such analysis, 45.7 mL of 0.500 M H2SO4 is required to neutralize 20.0 mL of
NaOH solution. What is the concentration of the NaOH solution?
Solution
Analyze We are given the volume (45.7 mL) and molarity (0.500 M) of an H2SO4 solution (the standard solution) that
reacts completely with 20.0 mL of NaOH solution. We are asked to calculate the molarity of the NaOH solution.
Plan Following the steps given in Figure 4.19, we use the H2SO4 volume and molarity to calculate the number of
moles of H2SO4. Then we can use this quantity and the balanced equation for the reaction to calculate moles of
NaOH. Finally, we can use moles of NaOH and the NaOH volume to calculate NaOH molarity.
Solve The number of moles of H2SO4 is the product of the volume and molarity of this solution:
Acids react with metal hydroxides to form water and a salt. Thus, the balanced equation for the neutralization
reaction is
Sample Exercise 4.16 Determining Solution Concentration by an
Acid–Base Titration
Continued
According to the balanced equation, 1 mol H2SO4 mol NaOH. Therefore,
Knowing the number of moles of NaOH in 20.0 mL of solution allows us to calculate the molarity of this solution:
Practice Exercise 1
What is the molarity of an HCl solution if 27.3 mL of it neutralizes 134.5 mL of 0.0165 M Ba(OH)2? (a) 0.0444 M,
(b) 0.0813 M, (c) 0.163 M, (d) 0.325 M, (e) 3.35 M.
Practice Exercise 2
What is the molarity of a NaOH solution if 48.0 mL neutralizes 35.0 mL of 0.144 M H2SO4?
Sample Exercise 4.17 Determining the Quantity of Solute by
Titration
The quantity of Cl– in a municipal water supply is determined by titrating the sample with Ag +. The precipitation
reaction taking place during the titration is
The end point in this type of titration is marked by a change in color of a special type of indicator. (a) How many
grams of chloride ion are in a sample of the water if 20.2 mL of 0.100 M Ag+ is needed to react with all the
chloride in the sample? (b) If the sample has a mass of 10.0 g, what percentage of Cl– does it contain?
Solution
Analyze We are given the volume (20.2 mL) and molarity (0.100 M) of a solution of Ag+ and the chemical equation
for reaction of this ion with Cl–. We are asked to calculate the number of grams of Cl– in the sample and the mass
percentage of Cl– in the sample.
(a) Plan We can use the procedure outlined by the green
arrows in Figure 4.17. We begin by using the volume
and molarity of Ag to calculate the number of moles
of Ag+ used in the titration. We then use the balanced
equation to determine the moles of Cl– in the sample
and from that the grams of Cl–.
Titration
Continued
Solve
From the balanced equation we see that 1 mol Ag+ mol Cl–. Using this information and the molar mass of Cl,
we have
(b) Plan To calculate the percentage of Cl– in the sample, we compare the number of grams of Cl– in the sample,
7.17 × 10–2 g, with the original mass of the sample, 10.0 g.
Solve
Titration
Continued
Comment Chloride ion is one of the most common ions in water and sewage. Ocean water contains 1.92% Cl–.
Whether water containing Cl– tastes salty depends on the other ions present. If the only accompanying ions are Na +,
a salty taste may be detected with as little as 0.03% Cl–.
Practice Exercise 1
A mysterious white powder is found at a crime scene. A simple chemical analysis concludes that the powder is a
mixture of sugar and morphine (C17H19NO3), a weak base similar to ammonia. The crime lab takes 10.00 mg of the
mysterious white powder, dissolves it in 100.00 mL water, and titrates it to the equivalence point with 2.84 mL of a
standard 0.0100 M HCl solution. What is the percentage of morphine in the white powder? (a) 8.10%, (b) 17.3%,
(c) 32.6%, (d) 49.7%, (e) 81.0%.
Practice Exercise 2
A sample of an iron ore is dissolved in acid, and the iron is converted to Fe 2+. The sample is then titrated with
47.20 mL of 0.02240 M MnO4– solution. The oxidation-reduction reaction that occurs during titration is
(a) How many moles of MnO4– were added to the solution? (b) How many moles of Fe2+ were in the sample?
(c) How many grams of iron were in the sample? (d) If the sample had a mass of 0.8890 g, what is the percentage
of iron in the sample?
Sample Integrative Exercise Putting Concepts Together
Note: Integrative exercises require skills from earlier chapters as well as ones from the present chapter.
A sample of 70.5 mg of potassium phosphate is added to 15.0 mL of 0.050 M silver nitrate, resulting in the formation
of a precipitate. (a) Write the molecular equation for the reaction. (b) What is the limiting reactant in the reaction?
(c) Calculate the theoretical yield, in grams, of the precipitate that forms.
Solution
(a) Potassium phosphate and silver nitrate are both
ionic compounds. Potassium phosphate contains
K+ and PO43– ions, so its chemical formula is
K3PO4. Silver nitrate contains Ag+ and NO3– ions,
so its chemical formula is AgNO3. Because both
reactants are strong electrolytes, the solution
contains, K+, PO43–, Ag+, and NO3– ions before
the reaction occurs. According to the solubility
guidelines in Table 4.1, Ag+ and PO43– form an
insoluble compound, so Ag3PO4 will precipitate
from the solution. In contrast, K+ and NO3– will
remain in solution because KNO3 is water soluble.
Thus, the balanced molecular equation for the reaction is
K3PO4(aq) + 3 AgNO3(aq) → Ag3PO4(s) + 3 KNO3(aq)
Continued
(b) To determine the limiting reactant, we must examine the number of moles of each reactant. (Section
3.7) The number of moles of K3PO4 is calculated from the mass of the sample using the molar mass as a
conversion factor. (Section 3.4) The molar mass of K3PO4 is 3(39.1) + 31.0 + 41(6.0) = 212.3 g ∕ mol.
Converting milligrams to grams and then to moles, we have
We determine the number of moles of AgNO3 from the volume and molarity of the solution. (Section 4.5)
Converting milliliters to liters and then to moles, we have
Comparing the amounts of the two reactants, we find that there are (7.5 × 10–4) / 13.32 × (0–4) = 2.3 times as
many moles of AgNO3 as there are moles of K3PO4. According to the balanced equation, however, 1 mol K3PO4
requires 3 mol AgNO3. Thus, there is insufficient AgNO3 to consume the K3PO4, and AgNO3 is the limiting
reactant.
Continued
(c) The precipitate is Ag3PO4, whose molar mass is 3(107.9) + 31.0 + 4(16.0) = 418.7 g / mol. To calculate the number
of grams of Ag3PO4 that could be produced in this reaction (the theoretical yield), we use the number of moles of
the limiting reactant, converting mol AgNO3 → mol Ag3PO4 → g Ag3PO4. We use the coefficients in the balanced
equation to convert moles of AgNO3 to moles Ag3PO4, and we use the molar mass of Ag3PO4 to convert the
number of moles of this substance to grams.
The answer has only two significant figures because the quantity of AgNO3 is given to only two significant figures.

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Lecture Presentation

© 2015 Pearson Education, Inc.

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• An electrolyte is a substance that dissociates

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• A strong electrolyte dissociates completely when

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AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)

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The molecular equation lists the reactants

AgNO3(aq) + KCl(aq)  AgCl(s) + KNO3(aq)

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Ag+(aq) + NO3−(aq) + K+(aq) + Cl−(aq) 

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In an acid–base reaction, the acid (H2O above)

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HCl(aq) + NaOH(aq)  NaCl(aq) + H2O(l)

H+(aq) + Cl−(aq) + Na+(aq) + OH−(aq) 

H+(aq) + OH−(aq)  H2O(l)

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 Some metathesis reactions do not give the

CaCO3(s) + 2 HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)

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Na2S(aq) + H2SO4(aq)  Na2SO4(aq) + H2S(g)

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• Loss of electrons is oxidation.

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• Elements in their elemental form have

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• Nonmetals tend to have negative

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• Nonmetals tend to have negative

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• The sum of the oxidation numbers in a

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Cu(s) + 2 Ag+(aq)  Cu2+(aq) + 2 Ag(s)

The reverse reaction does NOT occur. Why not? Aqueous

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• A solution of known concentration, called a

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Because Br– is a spectator ion, the net ionic equation is

Converting the volume of the solution to liters: